Removal of nine pesticide residues from water and soil by biosorption coupled with degradation on biosorbent immobilized laccase.

Biosorbents prepared with peanut shell and wheat straw were act as supports for the immobilization of Aspergillus laccase, and the redox mediator syringaldehyde (SA) was used to improve laccase-catalyzed degradation of nine pesticide residues, including isoproturon, atrazine, prometryn, mefenacet, penoxsulam, nitenpyram, prochloraz, pyrazosulfuron-ethyl and bensulfuron-methyl. Pesticides in water and soil samples were effectively removed via biosorbent concentration and subsequent immobilized laccase degradation on peanut shell or wheat straw supports. The Langmuir equation and Freundlich equation described the biosorption isotherms of the nine pesticides. Parameters that affect the degradation was also investigated. With concentration of pesticides and SA of 6.0 mg L-1 and 1 mmol L-1, over 54.5% and 65.9% of pesticides were removed in water in 3 days with a biosorbent immobilized laccase dose of 25 g L-1 for peanut shell immobilized laccase and wheat straw immobilized laccase, respectively. In the treatment of pesticide in soil with a biosorbent dose of 50 g (kg soil)-1, with the maximum degradation rates ranged from 20.9 to 92.9% and 14.7-92.0% in 7 days for peanut shell immobilized laccase and wheat straw immobilized laccase, respectively. Therefore, laccase immobilized on biomass materials has a strong potential for the effective removal of pesticide pollutants from water and soil by biosorption coupled with degradation.

Residue Analysis and Risk Assessment of Oxathiapiprolin and Its Metabolites in Cucumbers under Field Conditions.

In this study, a rapid, sensitive, and selective method was established for the detection of oxathiapiprolin and the metabolite IN-E8S72, as well as its glucose conjugate IN-SXS67 in cucumber using modified QuEChERS procedure combined with HPLC-MS/MS. The LOQs for all compounds were 0.02 mg kg-1, and the average recoveries were 77.4-111.3% with RSDs of 1.0-8.5%. Under the optimized conditions, the established method was successfully used to determine field samples in dissipation and terminal residue studies. The dissipation study results showed that oxathiapiprolin dissipated rapidly in cucumber with half-lives of 2.4-4.0 days. On the basis of the terminal residue results, the risk assessment was conducted, and both the international estimated daily intake (IEDI) or national estimated daily intake (NEDI) of oxathiapiprolin were much less than 100% which indicate a low health risk to consumers. This work provides guidance for establishing MRL of oxathiapiprolin in China and is of great significance for evaluating its dietary risk in cucumber.

Tebuconazole and Azoxystrobin Residue Behaviors and Distribution in Field and Cooked Peanut.

Residue behaviors of tebuconazole and azoxystrobin in field condition and the variation of their residue levels during the boiling process were evaluated. The terminal residues of peanut kernels were determined by using a modified QuEChERS method (quick, easy, cheap, effective, rugged, and safe) by means of the optimization of the novel purification procedure with multiwalled carbon nanotubes (MWCNTs) and Fe3O4-magnetic nanoparticle (Fe3O4-MNP) in the presence of an external magnetic field, and the terminal residues were all at trace level at harvest time. The residues in shells were detected as well to investigate the distribution in peanuts. Tebuconazole and azoxystrobin residue levels varied before/after boiling in kernels and shells to different degrees due to various factors, such as the modes of action and physicochemical properties of pesticides. The residues have been transferred from peanut into the infusion during boiling with the higher percentage of azoxystrobin as its lower logKow. The processing factors (PFs) for tebuconazole and azoxystrobin after processing were <1, indicating that home cooking in this study could reduce the residue levels in peanut. Risk assessment showed there was no health risk for consumers.

Comparison of micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction and modified quick, easy, cheap, effective, rugged, and safe method for the determination of difenoconazole in cowpea.

Two simple sample pretreatment for the determination of difenoconazole in cowpea was developed including micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction (ME-IL-VALLME) prior to high performance liquid chromatography (HPLC), and modified quick, easy, cheap, effective, rugged, and safe method (QuEChERS) coupled with HPLC-MS/MS. In ME-IL-VALLME method, the target analyte was extracted by surfactant Tween 20 micellar solution, then the supernatant was diluted with 3mL water to decrease the solubility of micellar solution. Subsequently, the vortex-assisted liquid-liquid microextraction (VALLME) procedure was performed in the diluted extraction solution by using the ionic liquid of 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF6) as the extraction solvent and Tween 20 as an emulsifier to enhance the dispersion of the water-immiscible ionic liquid into the aqueous phase. Parameters that affect the extraction have been investigated in both methods Under the optimum conditions, the limits of quantitation were 0.10 and 0.05mgkg-1, respectively. And good linearity was achieved with the correlation coefficient higher than 0.9941. The relative recoveries ranged from 78.6 to 94.8% and 92.0 to 118.0% with the relative standard deviations (RSD) of 7.9-9.6% and 1.2-3.2%, respectively. Both methods were quick, simple and inexpensive. However, the ME-IL-VALLME method provides higher enrichment factor compared with conventional QuEChERS method. The ME-IL-VALLME method has a strong potential for the determination of difenoconazole in complex vegetable matrices with HPLC.